Lubricating oils containing metal salts of a condensation product of a substituted phenol and a vinyl compound



Patented Oct. 20, 1953 UNITED STATE S P UF F'I CE LUBBICATING OILS CONTAINING:

' y SALTS 0F A.CONDENSATIONBPRODUUE.QF i SUBSTITUTED PHENOLHANDWAYVINYL "COMPOUND Loren. L.. Nefi, .Long vBeach, Galif;,iassi'gnor to .Unionfiil'company of Caliionnia LoszAngeles', Calif .21.. corporation-of California.

' N'o Drawing. Application 11113:. 1'7, 1950,v Serial-No. 174:3.67

vinylzcompoundsiandrtolubrieatinggoils containing suchimetal salts.

Thepresent trcnd internal combustion .611.- gin'es, .particularlyof :theydiesel engine :type, isin the direction ..ofihigher. compressioniratios', higher operating ltemperaturesiand thus. higherhorsa power output. "per, unit weight :of :the engine. Moreover, it is the i160 operate engines of. this type for;longerperiods;withouttoihchangeso that oils which'are satisfactory for'zuse in the present-day high output..diesel..engines,..ior .ex

ample, must have: not; only an initially high detergency and initially high anti=corrosion characteristics. bpt thesehproperti'es must .:.be";retained undersever conditionsrofuse .for'relativelyxlong,

periodsof use in anengine. To furthercomplb cate thepreparation oi'ra satisfactory oil for the;

lubrication of such; engines. the. fuels-available often contain higher proportions :of. :sulfurathan those: [which-have .been: used in the past and itis.

well. recognized: that high. sulfur. .fuels" tend to produce: corrosive.- conditions: in an engine which must be overcome by thexlubricatingt'oil employed, otherwise notonly does corrosion take place in the enginebutwearratesraresufliciently' high that frequent overhaul and replacement of parts becomes necessary, therebyunduly increasing: engine operation; cost.

In order to prepare oils. which: may be used in.

engines, of the character described it has been the practice to merely increase-thepercentage of.

additive. materials which have been. used, inxthe past in ordinarydiesel engines,;automotive *enginesand the like;, hoping toagainthe GXEIELQPID-L tectionnecessary byzthe. useof these larger proportions. i

It is an object of. this invention:to prepare' a lubricating oil which. will operatesatisfactorily in internal combustion engines and particularlyin the high output :diesel engines over relatively long-periods of service. It is another objectto prepare such lubricating oils which will protect engines of: this type:operatingundersevere conditions even while using aqfuel'containi'ngaas high as 1% or moreof sulfur;

It is round-that these and other objects can 3 of hydrohalogen. acidsxand. fatty. .acids.

be 'obtained by adding Ito :mineral lubricatingml.

relatively small amounts iof :an oil-soluble metal. salt i of the :condensation product. oifa .hydrocar bon substituted phenol-and vinyh compound .of .the' type described hereinb'elo w.

Thus thei'nvention residesuinclubricating zoils' contain-ing 'b'etween about; 0.05 :and :aloouttlO %1 or as *high as-about- 20% by:weight.ofi'annihsoluble meta-1 salt: of t'he1 condensation product robtained by condensing a hydrocarbon substituted phenol wherein the hydrocarbon substituentbr substituents contain. between about? 4 and: about 30 carbon: atoms with 'awinylicompoundi of. they class consisting .of. vinyl ethers: .andsvinyl J esters: These condensationzproducts are-acidic andrcapable of. reacting with metal'r basesrasiorexample. metal; oxides, hydroxides and: carbonates, undenappropriate conditions. to .form. .the. corresponding metalsalts. hydrohalogen. acids used'herein ini itszusual sense andincludes. hydrogen chloride, hydrogen brmnide hydrogen Jfluoride andhydrogeniodidei. Theseacidszmay also be termed hydrogen ::halides..

Atypical. oilesolublemetal salt. is produced by reacting approximately .one molecular proportion.

of:octy1 .phenoli with. one .=molecular proportion of vinyl acetate. The tphenoliandacetate are dissolved inzabout52i parts; Icy-volume of a petroleum naphtha. and 'tO".t'hBi. S01utiOIL is-added. about 2. parts by rvolume .ofa condensation catalyst, e. g.;. sulfuric acid; IIhecatalystis; added slowly -.andthe 'temperature. of the reaction. mixture isinaintainedzat aepoint suchgthatthe vinyl acetate is not vaporized: excessively. Preferably, because of .thedowjsboilinspomt ofuvinyl acetate, the .re-

action-is conducted under a. reflux condenser. Under any circumstance, by maintaining; a. temperature in. this instance-between about 30 'C. and. about 0 .C.. .the reaction proceeds rapidly andasmoothly and is:.comp1ete in approximately. 1.5,:t0p2 hours; SiIlGQat-he reactionaisi-exothermic,

completion-of the 31630131011: can. be determined. by

following the temperature of the reaction. mixture. Thus,.whereasduringtheearly part-of the reaction; cooling; is necessary order. to maintain the temperature within the-rrange .of. 30-

C. to 40"C.,.t0wardIthe:end of the reaction-heat.

maybe necessary in ordertoimaintain this-temp .peraturer Fo'llowingzthe completion:- ofuthe zreac tion the product is:ooo1ed=and wateriwashed' til free of mineral acidz. Uponevap'orationaof the solvent. naphtha employed: there remains: a; semisolid resin havingia brownishcolor- .The resin maybe convertedsinto its.;metaltsalt,i.as,for:-ex v ample the barium salt, by treatment of a solvent solution, as for example a naphtha, or a hydrocarbon lubricating oil solution of the resin with barium hydroxide octahydrate or with anhydrous barium hydroxide, in which latter case it is necessary to add small amounts of water during the neutralization. Where the metal salt is the desired product, the solvent solution of the condensation product is mixed with the desired metal base and, after neutralization and elimination of water, the solvent is evaporated leaving the metal salt of the condensation product. The barium salt of the above condensation product is a semi-solid to solid resin of brownish color. Where it is desirable to prepare a lubricating oil concentrate of the metal salt of the condensation product the neutralization is preferably effected in mineral oil solution. In this case the condensation product or the solvent solution of the condensation product is dissolved in about 1 to about 5 volumes of mineral oil and the desired metal base and water is added. The resulting product is agitated and heated sufiiciently to efiect complete neutralization and subsequently filtered to remove solid impurities. The resulting product will be referred to as an oil concentrate of an oil-soluble metal salt of the condensation product of a hydrocarbon substituted phenol and a vinyl compound of the class described.

Hydrocarbon substituted phenols which are useful in the preparation of the oil-soluble metal salts of this invention include the phenols having alkyl, cycloalkyl, aryl, aralkyl and alkaryl substituents. The substituents may be in the ortho-, metaor para-positions. Preferably the compound will have either an orthoand a paraposition free of substituents, or if the para-position is substituted then preferably both ortho positions should be free of substituents. Alkyl substituents include the butyl, amyl, iso-amyl, hexyl, heptyl, octyl, lauryl, cetyl and like radicals. These radicals may be normal or branched chain groups and the phenol may contain one or more of these substituents. Moreover, the alkyl substituents include the so-called wax radicals, i. e. radicals derived from parafin wax which may contain as high as or more carbon atoms. Wax phenols are well known in the art and may be prepared by reacting phenol with chlorinated parafiin wax in the presence of a Friedel-Crafts catalyst. Cycloalkyl substituents include cyclohexyl, methylcyclohexyl, cyclopentyl, methyl, ethyl and propyl cyclopentyl radicals and the like. Aryl radicals include the phenyl radical, as for example phenyl phenol. clude the benzyl radical and thus benzyl phenol. Alkaryl radicals include the radicals such as methylphenyl, ethylphenyl and the like.

Vinyl compounds which are useful in preparing the condensation products are the lower Aralkyl radicals inmolecular weight vinyl ethers, as for example The molar ratio of hydrocarbon substituted phenol to vinyl compound to be used in preparing desirable condensation productswillbe. be-

4 tween about 0.5 and about 3 to 1. Preferably this molar ratio will fall between about 0.8 and about 2 to 1. Particularly satisfactory results have been obtained using approximately equal molecular proportions of hydroxy compound and vinyl compound.

Catalysts or condensation agents which may be employed and which serve to effect the desired condensation reaction include the acid catalysts, as for example sulfuric acid and phosphoric acid, as well as the Friedel-Crafts type catalysts including aluminum chloride, boron tri fluoride, zinc chloride and the like. In the case of boron trifluoride, this compound is generally employed in the form of its complex with diethyl ether. The complex is known as boron trifiuoride etherate and has a boiling point of about C. The amount of catalyst to be employed will generally be between about 0.5% and 10% by weight of the total reactants. However, as much as 20% may be employed if desired, with satisfactory results.

Although the condensation reaction will take place in the absence of solventor diluent, it is generally desirable to employ a solvent during the condensation reaction. Solvents which may be employed include those which do not react with phenols or with the vinyl compounds under the conditions of condensation. Such solvents include the hydrocarbon naphthas or thinners, aromatic solvents, as for example benzene, toluene, and xylene, and the like as well as chlorinated solvents such as chloroform, carbon tetrachloride and the like. Also, the condensation is satisfactorily effected using mineral oil as the solvent or diluent. Thus, the solvent can be the oil to be used in the preparation of the final lubricating oil composition. The amount of sol vent or diluent to be employed may be widely varied, although generally between 0.5 and 5 volumes of solvent per volume of reactants is found to give satisfactory results.

The temperature of reaction will depend upon the reactants involved but will generally be between about 20 C. and about C. and preferably between about 0 C. and about 100 C. The temperature employed will depend to some extent upon the volatility of the vinyl compound employed. With the more volatile compounds, as for example vinyl chloride, lower temperatures are generally preferred and in this case particularly pressures of 1 to 3 or 4 atmospheres may be employed in order to maintain the reactants in solution or in liquid condition.

The time of reaction is dependent upon the particular reactants and upon the temperature and catalyst employed, although generally it is found that between about 1 hour and 4 or 5 hours sufiice to effect the desired extent of condensation. However, entirely satisfactory condensation products have been prepared when the reaction conditions were maintained for as long as 24 hours. Products so obtained are found to be oil-soluble and metal salts derived from the condensation products are also oil-soluble.

The metals to be employed in preparing metal salts are preferably the polyvalent metals, although the monovalent alkali metals are satisfactory in some instances. Thus the sodium, potassium and lithium salts are found to be oilsoluble and have the desired characteristics when added to mineral lubricating oils. Of the polyvalent metals, the alkaline earth metals calcium, magnesium, barium and strontium are particularly effective. However, the zinc, lead and emanate al uminum salts are suitable and insome cases chromium, iron, nickel; cobalt, mercury, tin and other polyvalent metalsalts have utility and areto be consideredpart of this invention, although this latter group of polyvalent metal salts are notto .be considered equivalent to the alkaline earth-metalsandzinc, lead and aluminum salts.

In preparing metal salts of'the condensation products asolvent solution or a lubricating oil solution of the condensation.produutisheated with the desired metal base, i; e. oxide, hydroxide or carbonate, in the presence of a small amount of water or in the presence of a small amount of alcohol. The mixture ;,isagitated and heated to eliminate water and efiect neutralization. In the-case of the more weakly basic metals the metal salt is preferably madeby-a method: involving first preparing the alkali metal salt, as for-exampl e the sodium salt, and subsequently metathesizing the alkali metal salt an organic salt of the desired metal. This metathesis is carried out in alcoholic solution=in or- 'der'='to prevent "hydrolysis whichwould- -occur aqueous solution. Methodsofmetathesizingayeah aci'ol salts are Well known-in theart and there- 1 foreneecl no=further descriptionhere; This-same method of preparation may -be--employed in "producing any of the*p'olyvalent metal salts-if so desired.

"In preparing finished lubricating oils the'oilsoluble-metal salts or theoil concentrates'thereof, produced as indicated-above, are added-to mineral lubricating oil in proportions such that the final oil will contain *between about 0.05%

and a-bout 20% and preferably between about 0.5 and %byweight ofthe salt. Although'no diflieulty is encountered in preparing oil-solutions becauseof the readyoil-solubilityor oildispersibility of these com-pounds, the solutions are generally prepared by heating the oil: containing the metal salt to'a temperature of 100 C. to 150 C. and agitatingthe solution to effect rapidandcomplete solution: and/or dispersion.

Lubricating oils which may be-employed includesubstantially all types of mineral lubricating-oils.

Thus 'the oilmay be one having a viscosity index of 0 or even loweror-it maybe aparafllnic type oil having a-viscosi-ty index the neighborhood of 100. Particularly satisfactory results have been obtained using a solvent treatedWestern paraffino mineral lubricating" oil having a vis cosity 1 index of between about 85-and 95.

Although lubricating oils containing the addi-- knownin the art, appear to. cooperate with the additivesyof this inventionto produce outstanding lubricating oils. Thus by .addingbetyeeen,..abo.ut

0.5 and 5% by weight-of a metalgpetroleumsule fonate it is found that the detergency of the oil is improved withoutadverselyafiecting the anticorrosion or anti-oxidation characteristics of .the oiL.

..Another detergent which. appears to :cooperate.

with-theadditivesof this. invention iszwmodifiedz sulfonate prepared .by heating an mllesoluble:7

metal petrcleumssulfonateiwithraniinorganica'baseJ Thus; 1

to solubiliZe the base the :sulf'onate. mahogan-y sulronic.acids:may:be:reacted withim organic -bases as, Lfor==examp1e, withimetal oxides;

5 hydroxides, carbonates:andibicarbonates,.torpro Such-:oil-soldble complexes of sulionic acidsand" metallhydroxides oxides, carbonates andrlthealike.

which may be employed together with=the=addi- 15; itive of this invention; are .those described by Mertes in U. S. Patents Nos. 2,501,731 and 137 1 Three different engine tests have been em ployed in'- the evaluation of lubricatingoils contaming-theoil soluble'metaisalts-ofthis -inventi'on; Thesetestshavebeen carried out in lnauson single cylinder engines, standard G cylinderChevrol'et engines and a single cylinder Caterpillar dieselstandard test engine. The tests are re-- :ferredto as the Lauson engine test, the Chevrolet'enginetest and the Caterpillar test, respectively.

'Tests in'the Liausonsingle cylinder test engines are-carried out such amanner that the oil is .-:subjected to severe service conditions. "Ihis test is employed to determine the-corrosiontendencies of the oil and to determine the tGHdGHGY-TOIWIIQ oil to deposit resinous and lacquer-like materials in theengine. in carrying out the Lauson 1 engine itest the engine is operated for a total of 60 hours undera load of about 3.5 horsepowenwith acoolant temperature of about 295 F. and an oiltemperature of about 280 F. At the endof -the test the cleanliness of-the engine is observed andthe 011' isgi-ven anumericaldetergencyrating between 0 and.- 100 where 100 indicates a perfectly I clean-engine.- Thuaadetergency rating of 100%- would indicate-thatduring the test witha given oilthereweresubstantially-no. lacquer or varnishlikedeposits withinthe engine. The -eorrosivity of the oil is measured by -determining the-loss :inweight of corrosion-sensitive copper-lead bearings duringtheperiod of test.

In those casesin whieh corrosion is extremely severeiandthereappearsto be danger of :engine failure due toexcessive corrosiono-r thebearings as indicated-by an examination made-at the 40- =hour period, the copper-lead bearings are are placedwithBabbitt bearings-in order to complete thefSO-hourtest. The results of such enginetests are shownin connection-with some of the examplespresented hereinbelow.

In the Chevroletengine'test the engine is op erated under a loadof about horsepower with a coolant temperature of aboutZQO -F. and an oi1 temperatureof about 280" F. This test -is-.used to evaluate corrosivity of A the lubricant. The loss diesel fuel. containing: 12%. by Wei h 1 f .fiulfl r- Generally, the bearingsare removedandweighed after 20-, and hours of operation.

.in weight of copper-lead bearings is determined "After 120..hours.and atithezendv ofthe test.a.nu;-

merical detergency rating" is assigned. The method of rating is similar to that employed in the Lauson engine test and 100% indicates a completely clean engine. Also the volume of carbon present in the top ring groove behind the ring is determined and this result is expressed at per cent by volume of the space behind the top ring at the start of the test.

The following examples illustrate some modifications of the invention, however it is to be realized that various modifications of the described methods of preparation and the described condensation product salts come within the scope of the invention.

Example I A 438 g. (2.12 mols) portion of octylphenol is dissolved in 710 ml. of a light paraflinc naphtha and to this solution is added 182 g. (2.11 mols) of vinyl acetate. This mixture is placed in a flask equipped with a stirrer, thermometer and reflux condenser.

Sulfuric acid (98% concentration) is added drop-wise through the reflux condenser until a total of 23.3 ml. (approximately 0.42 mols) has been added. During the initial addition the temperature rises to a point of rapid reflux (about 60 (3.), and the addition is continued at a rate such that refluxing continues. Following the addition of the sulfuric acid the mixture is heated at its reflux temperature for 2.5-3 hours and then cooled.

The product is washed with Water until free of acid and then dissolved in 2500 g. of an SAE 30 solvent extracted Western mineral lubricating oil and the mixture heated to 140 C. to vaporize the paraiiinic naphtha used as solvent in the initial reaction.

The product is converted into its barium salt by adding 187 g. of anhydrous barium hydroxide and 350 ml. of water. The water is added dropwise at 140 C. The resulting mixture is heated to 175 C., diluted with an additional 1000 g. of the same lubricating oil and filtered while hot using a filter aid. This product is an oil concentrate containing approximately 15.4% by weight of the barium salt of the condensation product of octylphenol with vinyl acetate. This product without further dilution operates satisfactorily in a Lauson engine, giving a high detergency and very low bearing weight losses.

A lubricating oil is prepared by dissolving 21.8 parts by weight of the above oil concentrate and about 3.7 parts by weight of an oil concentrate of calcium petroleum sulfonate in 74.5 parts by weight of the same SAE? 30 mineral lubricating oil described above. The resulting oil containing approximately 3.4% by weight of the barium salt and having a calcium sulfate ash due to calcium sulionate of approximately 0.24% is tested in a Caterpillar engine as described above, using a fuel containing 1% of sulfur. This oil has a detergency rating at 120 hours of 96% and at 240 hours of 96%. The percent of carbon in the top ring groove is 13 at 120 hours and 11 at 240 hours.

In comparison, the base oil without additives cannot be tested in this engine using a 1% sulfur fuel for the reason that the deposits are so great as to cause piston and ring sticking at far less than 120 hours to such an extent that it is impossible to complete the test. The base oil, 1. e. the oil without additives, run in the same engine using a low sulfur fuel has a detergency rating of approximately 55% at 120 hours.

Tests on the base oil, on the oil concentrate as produced above, and on the oil prepared for testing in the Caterpillar test engine are as follows:

Base Concentrate Oil T sted on (15.4% of in Cater- Barium Salt) pillar Engine Viscosity, SSU at:

Example II To 138 g. (0.67 mol) of octylphenol is added 57.6 g. (0.67 mol) of vinyl acetate. The mixture is stirred and cooled to 10 C. and concentrated sulfuric acid is added drop-wise to the mixture. A total of 7.3 ml. (0.13 mol) of the acid is employed. The temperature of the reaction mixture rises rapidly to 50 C. where violent boiling occurs. The sulfuric acid is added over a period of approximately 20 minutes and the reaction continued for approximately 3 hours, at which time the product is taken up in 500 ml. of benzene and Washed free of acid with water. The water-washed benzene solution is evaporated on a steam bath to remove the benzene and the product dissolved in 823 g. of the mineral lubricating oil described in Example I by heating the mixture with stirrin to 140 C. To the heated oil solution is added 100 g. of anhydrous barium hydroxide and ml. of water, the latter being added drop-wise, maintaining a temperature of about 140 C. When the neutralization is complete the product is heated to C. and filtered hot using a filter aid. The product has a sulfate ash of 8.4% and a soap number of 36.7 mg. KOH/g.

A lubricating oil is produced by dissolving a portion of the above product in mineral lubricating oil of the type described in Example I. The resulting oil contains 8.54% by weight of the product and has a sulfate ash of 0.72%. This oil tested in the Lauson engine has a detergency of 80% and bearing weight losses of 2, 12 and 64 mg. at 20, 40 and 60 hours, respectively.

A second lubricating oil is prepared which contains 4.27% by weight of the product of this example and approximately 3.2% of calcium mahogany sulfonate oil concentrate. This oil has a sulfate ash of 0.36% due to the octylphenol vinyl acetate condensation product salt and 0.21% due to calcium sulfonate. The oil employed is the same as that used above. Tests on this product in the Lauson engine show the oil to have a detergency of 79% and bearing weight losses of 90, 265 and 408 mg. at 20, 40 and 60 hours, respectively.

A Lauson engine test on the base oil without additives shows a detergency of 58% and bearing weight losses of 175 mg. and 500 mg. at 20 and 40 hours, respectively. Because of severe corrosion, in order to continue the engine operation for the required 60 hours the copper-lead bearings must be removed at 40 hours and replaced with Babbitt bearings.

Example III To 440 g. (2 mols) of nonylphenol dissolved in one liter of naphtha is added 40 ml. (46 g.) of boron trifluoride etherate. The resultin solution is heated to 30 C. and gaseous vinyl chloride is bubbled into the reactionmixture for ithe nonylphenol-vinyl chloride product.

m1; of water. andfiltered. This product is .an oil concentrate .three hours. at which. time ap roximately 12'? g.

naphtha.

Approximately.one third of the above product .isfheated to 125 and neutralized with. .cal-

cium hydroxide using 27g. of calcium hydroxide and approximatelyfifl m1. of water. The product is'heated; to 175C. andyfiltered. This prodnot is an oil concentrate, of the. calcium salt of condensation Approximately two-thirds of the condensation product in oil solution is neutralized. by treatment with '59.. gof sodium hydroxide and. 100 The product is heated to 200 C.

ofthe sodium, salt of the nonylphenol-vinylichloride condensation product.

Approximately one-half of the oil solution. of

"sodium salt as described in the preceding .paragraph is;diluted with .500 mLof. a lightpetroleum naphtha and to this solutionis added 100 g. of 'zinc chloride in 250 ml. of isopropanol. product is heated to evaporate the naphtha and The alcohol and. then filtered. This product. is. an

oil concentrate of the:zinc, salt of the. nonylphenol-vinyl chloride .condensation product.

Lubricating oils are preparedjby dissolving byweight 01 each of'the above .metal salt concentrates'in additional quantities of the mineral lubricating. oil described in Example '1. Enginetests on "these oils show that the condensation product salts impart both detergency and anticorrosion characteristics to the base oil.

EmampZe'IV "To 529. g. .(3. mols) of oecyclohex-ylphenol is I added 2 liters of alight petroleum thinner con- 'sisting primarily of-hexanes-and heptanes-and 180 g. (2.5mols) of. vinyl ethyl ether.

in Example ,I andthe .oil: solution. heatedto: evaporate hydrocarbon thinner.

Approximately. one-third of the? above oil .so-

lutionofcondensation product is treated with 123g. .olflead oxide and 10.0. ml. of water; The

.mixtureis heated. with stirring to 175 C...and then...filter.ed while hot, using a filter aid. The product is anoil concentrate of the lead salt .of

'o-cyclohexylphenol vinyl ethyl ether condensation'product.

ApproXimateIyone-third of the oil solution of the condensation product produced as above. is neutralized by treatment with freshly precipitate.d':magnesium hydroxide (32 g) as'a slurry in water. The mixture is heated with stirring to 1175.9 .67; andfilteredto yieldaan oilccncentrate of the: magnesium saltof .o eyclohex-ylphen'olevinyl hyl; ether condensation. product.

Thezremainins oneethirdincrtionior the-:oilzsolutionofathe. condensation; ypreductaproducedas above is neutralized withjlithium.hydroxideiusin approximately 14.6 g. of the. lithium hydroxide .monohydrate in 250 m1. of water. is. heated with stirring to. 100 C. and filtered move solids.

The mixture while hotto yield the corresponding lithium salt .in oil solution.

.Each .oi theabove metal salt concentrates, dissolved in mineralljlubricating, oil to give products containing approximately- 2% by weight of the metal. salt,flhave detergency and anti-corrosion characteristics similar to those of the oil prepared as described. in Example I.

Example- V .A paraffin 'wax having .anqaverage molecular weightpf about 350 *istreated; with. gaseous chlorine to, obtain a chlorinated paraffin wax containing-approximately'one; atom of'c'hlorine per molecule ofthewax; This productzis condensediwith phenol in the presence of anhydrous aluminum chloride to obtain awax substituted phenol having a molecular weight of approximately 450.

About 450 g. of the wax substituted phenol prepared as just described is mixed with 86 g; of vinyl acetate and 20 g. of concentrated sulfuric acid isadded to themixture slowly withstirring. The rate of addition is so controlled-that the-temperature of the reaction mixture is maintained between C. and C. After the addition of sulfuric acid is complete the reaction mixture is-maintained at about the same temperature'and stirred for an additional two hours. The product is dissolved in one liter ofpetroleum naphtha and water-washed to remove acid; The water- Washed product is neutralized 'with calcium hydroxide in the presence of a small amount of'water by refluxing thenaphtha solution for three hours. Excess water is removed by continuing the refluxing with a watertrap in the reflux line and the dehydrated solution is filtered to re- After evaporation of the naphtha the product consists of the calcium salt of awax substituted phenol-vinyl acetate condensation product.

.A lubricating oilprepared by'dissolving 6% by weight of the'aboveproduct in ans All 30mineral lubricating oil: having .a viscosity index of about 50 has good detergencyand exceptional anti-corrosioncharacteristics :as indicated by a bearing weight lossof less-than lDOrmg; in the Chevrolet engine test.

Example VI To. 170. g. of p-phenylphenol' in. solution in one. liter :of naphthaisadded 34 g. of boron-trifluoride .etherate. To thismixture is. added 86 g. of vinyl. isopropyl ether. The ether. is added slowly while maintaining. a temperature between 20f C. and 30 C.:and:whenxtheadditionuiscompletethemixtureis maintained at room. temperature .for. approximately three hours and then water washed to-remove condensation agent.

To theabove productisadded 1000 g. :01 mineral lubricating oiland the .oil: solution isneutralized with 94 .g. .of anhydrous barium hydroxide .using ml. of water. The. mixture is. heated slowly to C; toremoveesolvent andwat'er-and then filtered. The filtered product consistsoi an oil concentrate of the bariumsalt of aphenylphenol-vinylisopropyl ether condensation prodnot.

A lubricatinggoil containing approximately 10 by'weight: of. the above. oiliconcentrate operates satisfactorily in heavy duty-dieselrengine service.

Example VII.

A. 200 v.g. portion. of -.octylphenol dissolved in 1000. g.. ofv an SAE 10. solvent refined lubricating oil having a viscosity index of approximately 85 and to this solution is added 86 g. of vinyl acetate. The mixture is maintained at 75 C. and g. of concentrated sulfuric acid is slowly added. Heating and stirring is continued for approximately 10 hours, at which time the solution is water washed to remove acid.

The product is neutralized by treatment with 174 g. of barium hydroxide octahydrate and gradually heated to 175 C., at which temperature it is filtered. The filtrate is an oil concentrate of the barium salt of an octylphenol-vinyl acetate condensation product. This product, when dissolved in mineral lubricating oil to give an oil containing approximately 3% by weight of the barium salt, imparts detergency and anti-corrosion characteristics to the oil.

Example VIII To 305 g. of m-pentadecylphenol and 57 g. of vinyl acetate in solution in 1500 ml. of a light petroleum naphtha is added g. of concentrated sulfuric acid. The temperature of the reaction mixture rises rapidly to about 80 C. where refluxing occurs. This temperature is maintained for approximately 3 hours and the product then water washed.

The above condensation product is dissolved in 2500 g. of mineral lubricating oil as described in Example I and neutralized with 46 g. of lithium hydroxide monohydrate and 100 ml. of water. The product is heated to 175 C. to remove naphtha and water and filtered while hot. The resulting product is an oil concentrate of the lithium salt of a m-pentadecylphenol-vinyl acetate condensation product. This product, when dissolved in additional quantities of lubricating oil, imparts detergency and anti-corrosion characteristics to the oil.

Example IX Example VIII repeated using carbon tetrachloride in place of light petroleum thinner as the solvent results in a product substantially identical to that obtained with the thinner.

It is to be pointed out that the preceding examples are illustrative of the invention and are not to be considered as limiting because the phenols having one or more of the other hydrocarbon substituents described herein and other vinyl compounds described herein are found to condense under similar conditions to form comparable condensation products. Moreover, the other metals described herein as being useful in preparing the metal salts of the condensation products may be substituted for the metals employed in the examples to give salts which are effective as detergents and anti-corrosion agents when added to mineral lubricating oils. Furthermore, it is to be pointed out that an of the metals described as being useful for the preparation of metal salts of the condensation products are also useful in preparing metal sulfonates and metal sulfonate complexes which cooperate with the additives of this invention to produce noncorrosive lubricating oils of exceptionally high detergency. Such metal sulfonates or metal sulfonate complexes, when used in conjunction with the additives of this invention, are used in amounts between about 0.5% and about 10% based on the finished oil.

I claim:

1. A mineral lubricating oil containing between about 0.05 and about 20% by weight of an oilsoluble metal salt of the acidic condensation prod:

uct of a hydrocarbon substituted phenol, in which the hydrocarbon substituent contains between about 4 and about 30 carbon atoms, and a vinyl compound selected from the class consisting of divinyl ether, Vinyl ethyl ether, vinyl propyl ether, vinyl esters of hydrohalogen acids and vinyl esters of fatty acids containing between 1 and 6 carbon atoms in the fatty acid radical, said condensation product being obtained by condensing said phenol with said. vinyl compound in the molar ratio of between 0.5 and 3 to 1 at temperatures between about 20 C. and about 150 C.

2. A mineral lubricating oil containing between about 0.05 and about 20% by weight of an oilsoluble alkaline earth metal salt of the acidic condensation product of a hydrocarbon substituted phenol, in which the hydrocarbon substituent contains between about 4 and about 30 carbon atoms, and a vinyl compound selected from the class consisting of divinyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl esters of hydrohalogen acids and vinyl esters of fatty acids containing between 1 and 6 carbon atoms in the fatty acid radical, said condensation product being obtained by condensing saidphenol with said vinyl compound in the molar ratio of between 0.5 and 3 to 1 at temperatures between about 0 C. and about C. v

3. A mineral lubricating oil containing between about 0.05 and about 20% by weight of an oilsoluble alkali metal salt of the acidic condensation product of a hydrocarbon substituted phenol in which the hydrocarbon substituent contains between about 4 and about 30 carbon atoms and a vinyl compound selected from the class consisting of divinyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl esters of hydrohalogen acids and vinyl esters of fatty acids containing between 1 and 6 carbon atoms in the fatty acid radical, said condensation product being obtained by condensing said phenol with said vinyl compound in the molar ratio of between 0.5 and 3 to 1 at temperatures between about -20 C. and about C.

4. A mineral lubricating oil according to claim 1 in which the molar ratio of phenol to vinyl compound is between 0.8 and 2 to 1.

5. A mineral lubricating oil according to claim 2 in which said alkaline earth metal salt is a barium salt.

6. A mineral lubricating oil according to claim 2 in which said alkaline earth metal salt is a calcium salt.

7. A lubricating oil according to claim 3 in which said alkali metal salt is a lithium salt.

8. A lubricating oil according to claim 3 in which said alkali metal salt is a sodium salt.

9. A mineral lubricating oil containing between about 0.05% and about 20% by weight of an oilsoluble metal salt of the acidic reaction product obtained by condensing at a temperature between 0 C. and 100 C. a hydrocarbon substituted phenol in which the hydrocarbon substituent contains between about 4 and about 30 carbon atoms with vinyl actate using a molar ratio of phenol to vinyl acetate of between 0.8 and 2 to 1.

10. A mineral lubricating oil containing between about 0.05% and about 20% by weight of an oil-soluble metal salt of the acidic reaction product obtained by condensing cyclohexyl phenol with vinyl ethyl ether using a molar ratio of phenol to vinyl ethyl ether of between 0.8 and 2 to 1, the condensation being effected at temperatures between 0 C. and 100 C.

11. A mineral lubricating oil containing between about 0.05% and about 20% by weight of an oil-soluble metal salt of the acidic reaction product obtained by condensing a hydrocarbon substituted phenol in which the hydrocarbon substituent contains between about 4 and about 30 carbon atoms with vinyl chloride, at a temperature between about C. and about 100 0., using a molar ratio of phenol to vinyl chloride between 0.8 and 2 to 1.

12. A mineral lubricating oil containing between about 0.5% and about 10% by weight of the tween about 0.5% and about 10% by weight of the barium salt of the acidic condensation product obtained by condensing approximately equal molar proportions of octylphenol and vinyl acetate at temperatures between about 0 C. and about C.

14. A mineral lubricating oil according to claim 1 containing also between about 0.5% and about 10% by weight of an oil-soluble metal sulfonate.

15. A mineral lubricating oil according to claim 1 containing also between 0.5% and 10% of a modified sulfonate prepared by heating an oilsoluble metal sulfonate with an inorganic base selected from the class consisting of metal oxides, hydroxides, carbonates and bicarbonates to solubilize said base, said modified sulfonate having a ratio of equivalents of metal to equivalents of sulfonic acids between 1.1 and 3 to 1.

LOREN L. NEFF.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A MINERAL LUBRICATING OIL CONTAINING BETWEEN ABOUT 0.05 AND ABOUT 20% BY WEIGHT OF AN OILSOLUBLE METAL SALT OF THE ACIDIC CONDENSATION PRODUCT OF A HYDROCARBON SUBSTITUTED PHENOL, IN WHICH THE HYDROCARBON SUBSTITUTED CONTAINS BETWEEN ABOUT 4 AND ABOUT 30 CARBON ATOMS, AND A VINYL COMPOUND SELECTED FORM THE CLASS CONSISTING OF DIVINYL ETHER, VINYL ETHYL ETHER, VINYL PROPYL ETHER, VINYL ESTERS OF HYDROHALOGEN ACIDS AND VINYL ESTERS OF FATTY ACIDS CONTAINING BETWEEN 1 AND 6 CARBON ATOMS IN THE FATTY ACID RADICAL, SAID CONDENSATION PRODUCT BEING OBTAINED BY CONDENSING SAID PHENOL WITH SAID VINYL COMPOUND IN THE MOLAR RATIO OF BETWEEN 0.5 AND 3 TO 1 AT TEMPERATURES BETWEEN ABOUT -20* C. AND ABOUT 150* C. 